Humic Acids Of Different Origin Research Articles

ВИКОРИСТАННЯ ГУМІНОВИХ КИСЛОТ ДЛЯ МОДИФІКАЦІЇ БІОДЕГРАДАБЕЛЬНИХ ПЛІВОК, ВИГОТОВЛЕНИХ НА ОСНОВІ ПОЛІВИНІЛОВОГО СПИРТУ ТА ГІДРОКСИПРОПІЛМЕТИЛЦЕЛЮЛОЗИ

The article is devoted to the problem of obtaining packaging materials that combine a high level of gas and / or moisture resistance and strength with the ability to quickly decompose without harmful effects on the environment. The purpose of the research described in the article is to study the possibility of making such a material, which, during the period of use, will not only be resistant to the effects of various bacteria, but even prevent their appearance, and upon burial it will be biodegradable. The initial components, namely polyvinyl alcohol, hydroxypropyl methylcellulose, and humic acids of coal origin (as antibacterial additives) were reasonably selected. The modifying effect of humic substances obtained from three different samples of low-grade Ukrainian coal has been studied. In the course of the studies performed, it was found that humic acids of different origins and with different characteristics have a specific effect on the processes of structure formation in solutions of polyvinyl alcohol and hydroxypropyl methylcellulose. In particular, it was shown that in polyvinyl alcohol and methylcellulose solutions with the addition of humic acids that do not contain particles of carbon residues of various degrees of dispersion, an increase in the formation of an ordered structure is observed. Micrographs of solutions of polyvinyl alcohol and hydroxypropyl methylcellulose with humic acids are presented. The peculiarities of the influence of humic substances on the processes of structure formation of solutions of polyvinyl alcohol and hydroxypropyl methylcellulose have been investigated in order to obtain hybrid environmentally friendly biodegradable polymer films. The corresponding experimental-statistical mathematical models have been developed, they describe the dependence of the conditional viscosity and conductivity of polyvinyl alcohol and hydroxypropyl methylcellulose on the content of humic acids, the duration of preparation and one of the characteristics of the raw materials used to obtain humic acids. The corresponding equations are given. Keywords: biodegradable polymer films, coal, humic acids, polyvinyl alcohol, hydroxypropyl methylcellulose, experimental statistical mathematical models Corresponding author Zhang Siaobin, e-mail: shefuqinke1992@gmail.com

Study of the composition of humic acids of different origins

Study of the composition of humic acids of different origins

On the Probable Nature of Biological Activity of Humic Substances

It is common knowledge that humic substances extracted from different sources are characterized by high biological activity (BA), though the nature of this phenomenon is not quite clear up to now. To expand our understanding of the BA of humic substances, we studied the effect of humates prepared from humic acids of different origin on the germination of seeds. The efficiencies of seed treatment by humate solutions obtained from preliminary purified humic acids extracted from peat, coal, and soil differed insignificantly. At the same time, the solutions of salts of humic substances obtained via alkaline extraction from peat without subsequent purification did not lead to statistically significant biological effects. The analysis of literature and our own data allowed us to conclude that the biological activity of humic acids could be related to their capacity to regulate the growth processes via binding growth inhibitors released into the solution upon seed swelling into the supramolecular complexes.

Effects of Humic Acids Isolated from Peat of Various Origin on in Vitro Production of Nitric Oxide: a Screening Study.

A screening study of biological activity of native humic acids isolated from peat was performed; several physical and chemical parameters of their structures were studied by UV- and infrared spectroscopy. Spectroscopy yielded similar shape of light absorption curves of humic acids of different origin, which can reflect similarity of general structural principles of these substances. Alkaline humic acids have more developed system of polyconjugation, while molecular structures of pyrophosphate humic acids were characterized by higher aromaticity and condensation indexes. Biological activity of the studied humic acids was assessed by NO-stimulating capacity during their culturing with murine peritoneal macrophages in a wide concentration range. It was shown that due to dose-dependent enhancement of NO production humic acids can change the functional state of macrophages towards development of pro-inflammatory properties. These changes were associated with high activity of humic acids isolated by pyrophosphate extraction, which allows considering effects of isolation method on biological activity.

Bromination of humic acids of different origin

Data on the introduction of bromine atoms into the structure of humic acids isolated from the peat of Tver oblast and the brown coal of the Moscow Basin were generalized, and a comparative analysis of relevant methods was performed. It was shown that the test humic acids are similar in terms of structural parameters and demonstrate similar behaviors in the processes of bromination and hydrobromination. The dependences of the structural parameters of bromine-containing humic preparations on the mass fraction of bromine in them were obtained; correlations between the yields of humic preparations from the peat and the brown coal in the course of modifications were found; and the possible reaction paths of the bromination and hydrobromination processes were discussed. The biological activity of the bromine-containing humic preparations was tested, and its direct dependence on the mass fractions of bromine and phenolic hydroxyls in the humic preparations was found. It was shown that the modification of peat humic acids by hydrobromination is preferable for the production of biologically active humic preparations.

Surface Activity of Humic Acids Depending on Their Origin and Humification Degree

Abstract Humic substances are able to reduce the surface tension of their solutions and thus can act as surface-active substances in the natural environment, which may have industrial application. The ability to influence the surface tension of humic acid solutions depends on the origin of the humic acids. The objective of this study was comparison of the ability of humic acids of different origin (soil, water, peat, lignite etc.) to influence the surface tension of their solutions, and identification of the structural characteristics of peat humic acids that determine their surfactant properties. Industrially produced humic materials demonstrated no or insignificant impact on the surface tension of their solutions. However, humic acids isolated from peat had significant impact of the surface tension of their solutions, acting as weak surfactants. The surface tension of humic acid solutions decreased with increasing concentration, and depended on solution pH. Using a well-characterised bog profile, the ability to influence the surface tension of peat humic acids was shown to depend on age and humification degree. With increase of the humification degree and age, molecular complexity of humic acids and their ability to influence surface tension decreased; but nevertheless, the impact of the biological precursor (peat-forming bryophytes and plants) could be identified.

Study of the fragment composition of humic acids of different origin using IR-EXPERT software

Infrared spectra of humic acids have been studied using the IR-EXPERT computer system and database developed in the Novosibirsk Institute of Organic Chemistry. The information on the closest spectral analogues, their structures, and most probable structural fragments present in humic acid samples from Siberian peats and soils has been obtained.

Influence of humic acids of different origins on oxidation of phenol and chlorophenols by permanganate

The influences of humic acids (HAs) of different origins, including two commercial HAs, three soil HAs and one aquatic HA, on phenols oxidation by permanganate were studied. The apparent second-order rate constants of 2-chlorophenol (2-CP)/phenol oxidation by permanganate in the presence of HAs at pH 7 followed the order of commercial HA (Shanghai) > soil HAs > commercial HA (Fluka) > aquatic HA. Moreover, the commercial HA (Shanghai) could accelerate the oxidation of different chlorophenols (CP) significantly under neutral condition. The FTIR analysis demonstrated greater content of C C moieties and less amount of carboxylate, aliphatic groups and polysaccharide-like substances in soil HAs than in aqueous HA, suggesting that the increase of aromaticity in HA was beneficial to the oxidation of phenols by permanganate. The apparent second-order rate constants of 2-CP/phenol oxidation by permanganate in the presence of HAs correlated well with specific visible absorption (SVA) at 665 nm of HAs. High positive correlation coefficients ( R 2 > 0.75) implied that π-electrons of HA strongly influenced the reactivity of 2-CP/phenol towards permanganate oxidation, which agreed well with positive correlation between Fluorescence Regional Integration (FRI) and the apparent second-order rate constants. The π–π interaction between HAs and phenols, the steric hindrance effect and the dissociation of phenols may affect the oxidation of phenols by permanganate in the presence of HA at pH = 7.0.

Effects of humic acids on the growth of bacteria

The influence of humic acids of different origins on the growth of bacterial cultures of different taxa isolated from the soil and the digestive tracts of earthworms (Aporrectodea caliginosa)—habitats with contrasting conditions—was studied. More than half of the soil and intestinal isolates from the 170 tested strains grew on the humic acid of brown coal as the only carbon source. The specific growth rate of the bacteria isolated from the intestines of the earthworms was higher than that of the soil bacteria. The use of humic acids by intestinal bacteria confirms the possibility of symbiotic digestion by earthworms with the participation of bacterial symbionts. Humic acids at a concentration of 0.1 g/l stimulated the growth of the soil and intestinal bacteria strains (66 strains out of 161) on Czapek’s medium with glucose (1 g/l), probably, acting as a regulator of the cell metabolism. On the medium with the humic acid, the intestinal bacteria grew faster than the soil isolates did. The most active growth of the intestinal isolates was observed by Paenibacillus sp., Pseudomonas putida, Delftia acidovorans, Microbacterium terregens, and Aeromonas sp.; among the soil ones were the representatives of the Pseudomonas genus. A response of the bacteria to the influence of humic acids was shown at the strain level using the example of Pseudomonas representatives. The Flexom humin preparation stimulated the growth of the hydrocarbon-oxidizing Acinetobacter sp. bacteria. This effect can be used for creating a new compound with the elevated activity of bacteria that are destroyers of oil and oil products.

Humic acids of different origin as modifiers of cadmium-ion chemistry: A spectroscopic approach to structural properties and reactivity

The physical–chemical properties of humic acid fractions (HA) derived from urban sludge (CUS) and cattle manure (CCM) composts, and agricultural soil (FS) fertilised with sludge for ten years, were initially explored by elemental analysis, UV–Vis, FTIR and fluorescence. These properties were then compared with reference HA of terrestrial (SO) and aquatic (SR). To correlate the chemical properties and the reactivity of these HA, the binding of Cd(II) was investigated by fluorescence quenching techniques (FQ). Indeed, fluorescence spectroscopy has been proven to be a powerful tool in discriminating the origin, chemical features and degree of humification of naturally occurring organic matter. The HA compost exhibited higher N content, smaller molecular size and lower aromaticity than the reference HA. In addition, the CUS sample showed clear evidence of impurities, most likely of microbial origin, which was not evident in the FS sample ( i.e. during its further evolution/humification in soil). The quenching effect of Cd(II) is adequately described by a modified Stern–Volmer equation, which is based on two population fluorophores, one not being accessible. The resulting Cd–HA log K (conditional association constants) decreased in the order SO > CUS > FS > CCM > SR, thus reflecting the relative binding affinity. A similar order was found for the corresponding Cd(II) capacity, which is based on total Cd content in Cd-humate precipitates. Lastly, fluorescence analysis of the soluble and insoluble fractions clearly revealed the fluorophores most involved in the binding process. In conclusion, our work provides evidence that compost is a reservoir of “humic-like” material capable of compensating for any organic carbon deficit in soil and lessening the effect of inorganic pollutants.

Determination of OH groups in humic acids using methylation with dimethylsulfate

The methylation of humic acids (HA) with dimethylsulfate in acetone and methanol followed by the iodometric determination of the methoxy groups (Zeisel reaction) were applied to determine the contents of –OH groups in solid samples of HA of different origins. For the coal- and peat-derived HA samples, the contents of –OH groups determined after methylation in acetone ranged from 6.6 to 8.7 mmol/g, whereas the contents of –OH groups determined after methylation in methanol ranged from 4.0 to 5.0 mmol/g. These differences may be related to the content of carboxylic groups in the HA molecule that were not methylated in methanol, as confirmed by a comparison with results of conventional titrimetric determinations. Observed differences were interpreted as results of different polarity of both solvents and alkalinity of the reaction mixture during the methylation. The contents of alcoholic groups as well as some other minor –OH groups can be estimated using the –OH group contents obtained after methylation in both solvents together with the results of the conventional determinations of acidic functional groups. A repeatability of the –OH groups determination as estimated from a series of triplicate analyses of different HA samples ( n = 7) was in range of 0.15–0.73 mmol/g and 0.08–1.06 mmol/g (standard deviations) for methylation in acetone and methanol, respectively. Thus, the average repeatability of the –OH groups determination was estimated to be 0.38 and 0.50 mmol/g for methylation in acetone and methanol, respectively.

Characterization of humic substances of different origin by means of mass spectrometry and neural networks

Mass spectrometry fingerprinting of humic acids extracted from different soils has been carried out using laser desorption/ionization mass spectrometry (LDI-TOF MS). LDI-TOF MS provides characteristic mass spectra fingerprints for the humic acids of different origin. The information given in the fingerprints was evaluated for natural grouping trends in the samples by neural networks computing tools, such as self-organizing feature map (SOFM). This approach is efficient for recognizing patterns in the humic acids samples independently of their characteristic variability; variability characterizing natural products such as humic substances. The use of multi-layer perceptron artificial neural networks gave a successful classification of the samples.

Influence of inorganic soil components and humic substances on the mechanochemical removal of pentachlorophenol

The influence of the presence of humic acids of different origin on the catalytic transformation of pentachlorophenol (PCP) by two metal oxides, ferrihydrite and birnessite, using mechanochemical contact was studied. The mechanochemical dry contact with light grinding of PCP and birnessite was more effective than that observed in the presence of ferrihydrite (approximately 70 and 40% of PCP removal after 20 days, respectively). The removal of PCP by birnessite and ferrihydrite was significantly enhanced in the presence of humic acid (HA). The different origin of humic acids (agricultural, forest and commercial) showed a slight influence on the overall reaction. The commercial HA, when mixed with birnessite, was more effective in reducing PCP concentration compared to the others two HAs investigated. The transformation process in the presence of birnessite with and without HA was accompanied by the release of four chlorides per molecule of PCP transformed.

Caracterização de ácidos húmicos de diferentes origens por eletroforese capilar de zona

O objetivo deste trabalho foi caracterizar ácidos húmicos (HA) de diferentes origens por eletroforese capilar de zona (CZE) e avaliar a influência da concentração do tampão borato nesta caracterização. Os resultados mostraram que HA de diferentes origens podem ser rapidamente caracterizados por CZE. Por esta técnica, a caracterização de HA é devido a diferenças na razão carga/tamanho e das propriedades dos componentes individuais, conseqüência de suas diferentes origens.

Capillary zone electrophoresis of humic acids from the American continent.

A multicomponent background electrolyte (BGE) was developed and its composition optimized using artificial neural networks (ANN). The optimal BGE composition was found to be 90 mM boric acid, 115 mM Tris, and 0.75 mM EDTA (pH 8.4). A separation voltage of 20 kV, 20 degrees C and detection at 210 nm were used. The method was applied to characterize several humic acids originating from various countries of the American continent: soil (Argentina), peat (Brazil), leonardite (Guatemala and Mexico) and coal (United States). Comparison with humic acids of International Humic Substances Society (IHSS) standard samples was also done. Well reproducible electropherograms showing a relatively high number of peaks were obtained. Characterization of the samples by elemental analysis and UV spectrophotometry was also done. In spite of the very different origins, the similarities between humic acids are high and by matrix assisted desorption/ionization-time of flight (MALDI-TOF)-mass spectrometry it was shown that most of the m/z patterns are the same in all humic acids. This means that humic acids of different origin have the same structural units or that they contain the same components.

Comment on “The study of americium, yttrium and lead complexation by humic acids of different origin” by A. Paulenova et al., JRNC, 246 (2000) 617

Comment on “The study of americium, yttrium and lead complexation by humic acids of different origin” by A. Paulenova et al., JRNC, 246 (2000) 617

Fluorescence of Humic Acids (HA) and Pyrene-HA Complexes at Ultralow Temperature

The interaction of pyrene with humic acids of different origins was investigated using fluorescence line narrowing (FLN) spectroscopy at 10 K. FLN spectroscopy can be used to obtain vibrationally resolved fluorescence spectra from samples that under ordinary conditions suffer from extensive spectral broadening. Due to the presence of humic acid the site distribution and the relative intensities of the ground-state vibrations in the fluorescence spectrum (Ham-effect) of pyrene were changed. Both effects were related to the altered microenvironment of pyrene in the presence of humic acid. On the other hand, for humic acids no fluorescence line narrowing effect was observed indicating the occurrence of intra- and intermolecular processes.

The Study of Americium, Yttrium and Lead Complexation by Humic Acids of Different Origin

Complexation equilibrium of metals by three humic acids of different origin with ultrafiltration method was investigated at pH 4 a 5 and ionic strength I = 0.1M NaClO4. Commercial (Aldrich) and two original humic acids (peat and soil, obtained by six step isolation process from the material from Trnava county, close to the NPP Jaslovske Bohunice) were used in this study. For the evaluation of the results, the model of metal ion charge neutralization upon humic acid functional group proposed by the Kim and Czerwinski was used. Complexation constants were calculated using the terms of this model (operational concentration, loading capacity). The values of log β = 5.39±0.16 for yttrium, 6.15±0.16 for americium and 5.20±0.08 for lead were found. Correlation of free metal concentration and ratio of molar fraction of complexing functional groups confirms the validity of charge neutralisation model for metal and polyelectrolyte complexation study.

Triallate adsorption onto humic acids of different origin and nature

Humic acids (HAs) isolated from two different soils sampled at two different depths and from a pig slurry used as soil amendment, and their interaction products with the herbicide triallate were characterized by elemental and functional group analyses and Fourier transform infrared (FT-IR), electron spin resonance (ESR) and fluorescence spectroscopy in the emission, excitation and synchronous scan modes. The pig slurry HA exhibited a greater aliphatic character, higher presence of proteinaceous and polysaccharide constituents, lower acidic functional group content, and lower aromatic polycondensation and humification degrees than soil HAs. Only small differences occurred between HAs from the two soil types and the two sampling depths of each soil. Adsorption of triallate onto HAs, measured using a slurry-type method combined with high-pressure liquid chromatography (HPLC), could be described in all cases by linear isotherms. The extent of adsorption of triallate onto pig slurry HA was between two and four orders of magnitude higher than that onto soil HAs. The types of binding mechanisms appeared to be related to the compositional, structural and functional properties of the HA. Hydrophobic bonds possibly prevailed in the interaction of triallate with pig slurry HA, whereas adsorption of triallate onto soil HAs possibly involved charge-transfer and ionic bonds, with the participation of fluorophore groups of the HA macromolecules.

Humic acid capillary zone electrophoresis adsorption on capillary walls, separation in metal ion supplemented buffer and the fingerprints.

Capillary zone electrophoresis (CZE) in quartz tubes is often being used for the separation and characterization of humic acids (HA). A method was found to follow adsorption (and kinetics) of humic acids on a fused-silica capillary wall. It was shown that the adsorption of humic acids on an uncoated capillary wall is high. The effect on sorption of additives to the background electrolyte (BGE) was studied. Sorption can be eliminated by adding magnesium(II) salts (14-50 mM) to the BGE (pH 3.40) with resultant highly reproducible electropherograms as well as detailed and expressive fingerprints for HA of different origin.